Method of plasmon-enhanced properties of materials and applications thereof

ABSTRACT

Methods and applications of surface plasmon resonance-enhanced antibacterial, anti-adhere, adhere, catalytic, hydrophilic, hydrophobic, spectral change, biological and chemical decomposition properties of materials with embedded nanoparticles are disclosed. A method of the nonlinear generation of surface plasmon resonance enables the use of light with wavelengths from X-Ray to IR to enhance properties of materials by several orders of magnitude. The nanoparticle size is crucial for the enhancement and their size is considered to be in the proposed methods and applications within a range of 0.1 nm to 200,000 nm. The nanoparticles preferably are made of noble metals and/or semiconductor oxides. The invention describes a very broad spectrum of applications of surface plasmon resonance-enhanced properties of materials with embedded nanoparticles, from environmental cleanup by road pavement and construction materials, self-cleaning processes of surface materials, thermochromic effects on heat blocking materials, corrosion preventing paint, to sanitization by antibacterial textile fabrics, filters, personal clothing, contact lenses and medical devices.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is related to U.S. Provisional Patent Application No.60/539,192 entitled “Plasmon Enhanced Antibacterial Materials and TheyUse” filed Jan. 27, 2004, U.S. Provisional Patent Application No.60/551,389 entitled “Medical Devices Having Plasmon EnhancedDiagnostics, Biomolecule Antiadhere and Antibacterial Materials Thereon”filed Mar. 10, 2004, and to U.S. Provisional Patent Application No.60/559,059 entitled “Photocatalytic and Hydrophilic Properties ofMaterials Induced by Surface Plasmons and Application Thereof.” filedApr. 5, 2004 which are herein incorporated by reference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH

There is NO claim for federal support in research or development of thisproduct.

FIELD OF THE INVENTION

The herein disclosed invention finds applicability of nanotechnology inthe field of environmental cleanup, sanitization and quality of humanhealth.

BACKGROUND OF THE INVENTION

Photoinduced properties of materials embedded with semiconductor oxideswere reported in several patents and papers (U.S. Pat. Nos. 6,194,346,6,074,981, 6,455,465, 6,524,664, Mor, et al., “A room-temperatureTiO2-nanotube hydrogen sensor able to self-clean photoactively fromenvironmental contamination”, J. Mater. Res., Vol. 19, No. 2, (2004),Benedix, et al., “Application of Titanium Dioxide Photocatalysis toCreate Self-Cleaning Building Materials”, Lacer, No.5, (2000), Paz, etal., “Photooxidative self-cleaning transparent titanium dioxide films onglass”, J. Mater. Res., Vol. 10, No. 11, p. 2842, (1996)). All of thesemethods and results presented in patents and papers are based on theultraviolet light photodecomposition of the semiconductor oxidesdeposited on the material surfaces that change the physical and chemicalproperties of these materials. These patents and papers do not teach howto use other wavelengths than UV light and how to use surface plasmonresonance-enhanced effects, nanotechnology advances, and other compoundslike noble metals to enhance properties of materials. There were alsosuccessful attempts of blue light catalytic effects of semiconductoroxides deposited on material surfaces induced (U.S. Pat. Nos. 6,139,803,5,874,701). In that case, the semiconductor oxides were embedded tomaterials which they change the semiconductor oxides ultraviolet lightabsorption band to the blue light band. However, these materials displaysubstantially reduced photocatalytic properties that limit them to beused in many applications. Again, these inventions do not teach how touse surface plasmon resonance-enhanced effects, nanotechnology advances,and other compounds like noble metals to enhance properties ofmaterials.

Researchers from Hanyang University, South Korea incorporate nano-sizedsilver particles into polypropylene to produce an anti-microbialmaterial that could be used in anything from carpets, to napkins andsurgical masks (http://www.materials-edge.net/html/print.php?sid=95).Silver has been medically proven to kill over 650 disease-causingorganisms in the body and is also very safe. By combining silver andpolypropylene to produce an organic-inorganic fiber, researchers haveproduced the first safe, anti-microbial fiber with a wide range ofpossible applications. The researchers used nano-sized silver particlesto maximizing the surface area and give the optimum antibacterialeffect. They found that the fibers containing silver in the core parthad no antimicrobial activity and the fibers that included silver in thesheath part showed excellent antibacterial effect. However, thisresearch does not show how to use surface plasmon resonance or othertypes of energy to significantly enhance antibacterial of textilefabrics, how to induce anti-microbial properties of fiber with embeddedmetal nanoparticles under fiber surface.

There are a few inventions related to antibacterial materials in whichsilver is embedded to these material fibers (U.S. Pat. Nos. 6,584,668,6,087,549, 5,985,301, 5,876,489, 4,340,043). However, in these patentsthere is no mention of enhancing antibacterial properties of materialsinduced by plasmon resonance or other types of energy, how to use metalsother then silver or metal oxides with antibacterial properties offabrics, what crucial role play the size and shape of embedded metalnanoparticles to fabrics on antibacterial properties of these fabrics.

There is also great need for “smart materials”, e.g. materials whoseproperties would be altered upon changes of physical parameters ofenvironment surrounding these materials (T. Manning and I. Parkin,“Atmospheric pressure chemical vapour deposition of tungsten dopedvanadium(IV) oxide from VOCl₃, water and WCl₆ ”, J. Mater. Chem.,2554-2559 (2004), U. Qureshi et al., “Atmospheric pressure chemicalvapour deposition of VO₂ and VO₂/TiO₂ films from the reaction of VOCl₃,TiCl₄ and water”,J. Mater. Chem., 1190-1194, (2004)). Currently, thereis a very modem success of applying the method of surface plasmonresonance to “smart materials” (Y. Sun and Y. Xia, “IncreasedSensitivity of Surface Plasmon Resonance of Gold Nanoshells Compared toThat of Gold Solid Colloids in Response to Environmental Changes”, Anal.Chem., 74,5297-5305 (2002); Cao, Y.; Jin, R.; Mirkin, C. A. J. Am. Chem.Soc., 123, 7961 (2001)). The observed, in these reports, surface plasmonresonance-enhanced spectral changes upon changing environment ofsurrounding materials are within 50 nm. In this method, theenvironmentally sensitive polymer covering metal nanoparticles altersits own properties upon changes in the environment, which leads tospectral changes of a SPR absorption band. These modest spectral changesare good enough to built biochemical sensors, but not sufficient toapply them in “smart materials”, where drastic spectral changes would bedesired. For example, there is great need to observe spectral changes bya few hundreds nanometers in glass windows upon sunlight heat, which cancause blocking infrared sunlight by glass window when temperature of theglass is to high. Hence, there is great need for new methods whichsignificantly would change properties of materials. The disclosed belowinvention shows a novel methodology how to enhance properties ofmaterials by many orders of magnitude, to overcome limitations ofconventional methods and provides novel applications of surface plasmonresonance-enhanced photocatalytic and other properties of materials.

References

The following are patents found that may be associated within the hereindisclosed invention.

U.S. Patent Documents

U.S. Pat. No. 6,194,346 February 2001 Tada, et al. U.S. Pat. No.6,074,981 June 2000 Tada, et al. U.S. Pat. No. 6,455,465 September 2002Miyasaka U.S. Pat. No. 6,524,664 February 2003 Hashimoto, et al. U.S.Pat. No. 6,139,803 October 2000 Watanabe, et al. U.S. Pat. No. 5,874,701February 1999 Watanabe, et al. U.S. Pat. No. 6,584,668 July 2003 Green,et al. U.S. Pat. No. 6,087,549 July 2000 Flick U.S. Pat. No. 5,985,301November 1999 Nakamura, et al. U.S. Pat. No. 5,876,489 March 1999Kunisaki, et al. U.S. Pat. No. 4,340,043 July 1982 Seymour

Other References

-   Mor, et al., “A room-temperature TiO2-nanotube hydrogen sensor able    to self-clean photoactively from environmental contamination”, J.    Mater. Res., Vol. 19, No. 2, (2004) Benedix, et al., “Application of    Titanium Dioxide Photocatalysis to Create Self-Cleaning Building    Materials”, Lacer, No.5, (2000)-   Paz, et al., “Photooxidative self-cleaning transparent titanium    dioxide films on glass”, J. Mater. Res., Vol. 10, No. 11, p. 2842,    (1996)-   http://www.materials-edge.net/html/print.php?sid=95-   T. Manning and I. Parkin, “Atmospheric pressure chemical vapour    deposition of tungsten doped vanadium(IV) oxide from VOCl₃, water    and WCl₆ ”, J. Mater. Chem., 2554-2559 (2004)-   U. Qureshi et al., “Atmospheric pressure chemical vapour deposition    of VO₂ and VO₂/TiO₂ films from the reaction of VOCl₃, TiCl₄ and    water”,J. Mater. Chem., 1190-1194, (2004)-   Y. Sun and Y. Xia, “Increased Sensitivity of Surface Plasmon    Resonance of Gold Nanoshells Compared to That of Gold Solid Colloids    in Response to Environmental Changes”, Anal. Chem., 74,5297-5305    (2002)-   Cao, Y.; Jin, R.; Mirkin, C. A. J. Am. Chem. Soc., 123, 7961 (2001)-   M. Kerker, “Optics of colloid silver”, J. Colloid Interface Sci.    105, 298 (1985)-   Lakowicz et al, “Intrinsic fluorescence from DNA can be enhanced by    metallic particles”,-   Biochem. Biophys. Res. Comm. 286, 875 (2001)-   Gryczynski et al., “Multiphoton excitation of fluorescence near    metallic particles: enhanced and localized excitation”, J. Phys.    Chem. B, 106, 2191 (2002)-   M. Moskovits: Rev. Mod Phys. 57, 783 (1985)-   T. L. Haslett, L. Tay, M. Moskovits: J. Chem. Phys. 113, 1641    (2000), and references therein-   K. Kneipp, Y. Wang, H. Kneipp, L. T. Perelman, I. Itzkan, R. R.    Dasari M. S. Feld: Phys. Rev. Lett. 78, 1667 (1997)-   Ditlbacher H. et al., Appl. Phys. B 73, 373-377 (2001)-   Hirsch et al., PNAS, 100, 13549-13554 (2003)-   S. Coyle, et al., Phys. Rev. Let. 87(17), 176801, (2001)-   N. Bloembergen, “Laser-induced electric breakdown in solid”,    IEEE. J. Quan. Electron., 10, pp.375-386 (1974)-   D. Stern, R. W. Schoenlein, C. A. Puliafito, E. T. Dobi, R.    Biringruber, J. G. Fujimoto, “Corneal ablation by nanosecond,    picosecond, and femtosecond lasers at 532 and 625 nm”, Arch.    Ophthalrnol., 107,587-592 (1989)

SUMMARY DESCRIPTION OF THE PATENT

Methods and applications of surface plasmon resonance-enhancedphotocatalytic, hydrophilic/hydrophobic, antibacterial, anti-microbial,anti-adhering/adhering, spectral change, biological and chemicaldecomposition properties of materials with the embedded nanoparticlesare disclosed in a present invention. In the embedded nanoparticles,under excitation of electromagnetic radiation and/or under other formsof energy, are generated extremely strong surface plasmon resonanceelectromagnetic fields, ultrasound, heat and other types of energy,which interact with the nearby chemical and biological molecules andwith the material. The enhancement of these interactions is fromhundreds to millions times and more. The nonlinear generation of surfaceplasmon resonance combined with nonlinear optical excitation enable theuse of a broad spectrum of light within a range of 0.001 nm to 20,000 nmin the proposed methods and applications. The embedded nanoparticlesizes are crucial to the proposed surface plasmon resonance enhancementsand their sizes are considered to be within a range of 0.1 nm to 200,000nm. In the present invention the use of the embedded nanoparticles madeof noble metals and/or semiconductor oxides is also preferable, in whichthe enhancement effects are very evident and mechanism of theinteractions with surrounding molecules and the material is lessdifficult to explain. There is very broad spectrum of applications forthe proposed methods in the present invention, from environmentalcleanup by embedding the nanoparticles to road pavement materials orconstruction materials, to antibacterial properties of textile fabrics,filters, personal clothing, contact lenses, and medical devices.

FIGURES DESCRIPTION

FIG. 1. shows photocatalytic reactions of a metal oxide molecule (MX)and water molecule in the presence of light. Light breaks the metaloxide molecule (MX) to a metal (M) and non-metal species. The metal (M)under light absorption generates surface plasmon resonance (SPR) andinteracts with nearby environment attracting electron unsaturatedmolecules like water. The non-metal species interact with nearbymolecules.

FIG. 2. shows a photocatalytic reactions of a metal (M) and watermolecule in the presence of light. The metal under light absorptiongenerates surface plasmon resonance (SPR) and interacts with nearbyenvironment attracting electron unsaturated molecules like water.

FIG. 3. shows a surface plasmon resonance (SPR)-induced hydrophilicityof a metal (M) in the presence of water molecules and light. The metalunder light absorption generates SPR and interacts with nearbyenvironment attracting electron unsaturated molecules like water.

FIG. 4. illustrates areas of a surface plasmon resonance (SPR)-inducedhydrophilicity and hydrophobicity of a material.

FIG. 5. illustrates a surface plasmon resonance (SPR)-inducedanti-adhering properties of a material. The nanoparticle excited by SPRis negatively charged and repel negatively charged biomolecule.

FIG. 6. shows a thermochromic dissociation reaction of a metal complex(MX) under SPR absorption of another metal (N) and/or the metal complexand higher temperature, and a thermochromic redissociation of anon-metal ligand (X) with the metal (N) under higher temperature. Thebottom part of this figure shows absorption spectra of chemicalcomponents in these SPR-induced thermochromic reactions.

FIG. 7. shows a thermochromic dissociation reaction of a metal complex(MX) under SPR absorption of another metal (N) and/or the metal complexand higher temperature, and a thermochromic redissociation of anon-metal ligand (X) with a metal (M) under SPR absorption and lowertemperature. The bottom part of this figure shows absorption spectra ofchemical components in these SPR-induced thermochromic reactions.

FIG. 8. shows one of many examples of a chemical enhancement ofSPR-enhanced properties of materials. Hydrogen peroxide interacts withmetal nanoparticles (M) in the presence of SPR and light. The hydrogenperoxide molecules will decompose to water molecules which under SPRwill make complexes with the metal nanoparticles (M) and the releasedatomic oxygen molecules will very aggressively oxidize nearby molecules.Hence, the hydrophilicity and highly oxygenation properties of materialwill be created.

DETAIL DESCRIPTION OF THE INVENTION 1. Abbreviations and Definitions

-   CW optical source—continuous waves source-   SPR-surface plasmon resonance generated in a nanoparticle under    illumination by electromagnetic radiation and other forms of energy-   one-photon mode of excitation—process in which molecule is excited    by a one photon absorption event-   two-photon mode of excitation—process in which molecule is excited    by simultaneous absorption of two photons-   multi-photon mode of excitation—process in which molecule is excited    by simultaneous absorption of three or more photons-   step-wise mode of excitation—process in which molecule is excited by    absorption of one photon and subsequently by absorption of second    photon-   up-conversion mode of excitation—process in which a molecule is    excited by lower energy photon than energy of the lowest excited    state of the molecule-   metal island—a nanoparticle on a substrate without defined shape-   thermochromic reaction—a reaction which undergoes a temperature    change and is associated with a spectral change.

2. Exemplary Embodiments

Although the following detailed description contains many specifics forthe purposes of illustration, anyone of ordinary skill in the art willappreciate that many variations and alterations to the following detailsare within the scope of the invention. Accordingly, the followingembodiments of the invention are set forth without any loss ofgenerality to, and without imposing limitations upon, the claimedinvention.

The present invention provides a novel methodology and applications thatovercome limitations of conventional methods of using UV light and metaloxides for inducing photocatalytic and other properties of materials.

The invention relates to scientific findings of the surface plasmonresonance (SPR)-enhanced interaction between metal nanoparticles andnearby molecules, which were published in few scientific reports (M.Kerker, “Optics of colloid silver”, J. Colloid Interface Sci. 105, 298(1985); Lakowicz et al, “Intrinsic fluorescence from DNA can be enhancedby metallic particles”, Biochem. Biophys. Res. Comm. 286, 875 (2001);Gryczynski et al., “Multiphoton excitation of fluorescence near metallicparticles: enhanced and localized excitation”, J. Phys. Chem. B, 106,2191 (2002)). In these reports, researchers used the fluorophores(mostly organic laser dyes) to visualize or test the SPR-enhancedinteractions. Their studies show that the fluorescence intensity of thefluorophores located nearby metal nanoparticles can be enhanced by afactor as high as ˜10⁴ with one-photon mode of excitation and ˜10⁸ withtwo-photon mode of excitation, and Raman signal for fluorophores whichare in contact with metal nanoparticle can be enhanced by ˜10¹⁴ (M.Moskovits: Rev. Mod. Phys. 57, 783 (1985); T. L. Haslett, L. Tay, M.Moskovits: J. Chem. Phys. 113, 1641 (2000), and references therein; K.Kneipp, Y. Wang, H. Kneipp, L. T. Perelman, I. Itzkan, R. R. Dasari M.S. Feld: Phys. Rev. Lett. 78, 1667 (1997); Gryczynski et al.,“Multiphoton excitation of fluorescence near metallic particles:enhanced and localized excitation”, J. Phys. Chem. B, 106, 2191 (2002)).The observed SPR-enhanced interaction of metal nanoparticles withfluorophores was also associated with intense decomposition offluorophores when fluorophores where at a distance of 20 nm or less frommetal nanoparticles (Ditlbacher H. et al., Appl. Phys. B 73, 373-377(2001)).

The present invention expands the above scientific findings to newmethods and new applications of the SPR-enhanced interactions ofnanoparticles embedded into a material with the nearby biological andchemical substances and with the material. The SPR excited nanoparticlesinteract extremely strong with the substances that are in direct contactwith them. In the contact, SPR-enhanced interactions usually lead todecomposition of these substances. In the direct contact interactions,the nanoparticles play mostly a catalytic role. The SPR excitednanoparticles also interact with nearby molecules which are not indirect contact with them. At nearby distances from the SPR excitednanoparticles exist very intense SPR electromagnetic fields (plasmons)(Ditlbacher H. et al., Appl. Phys. B 73, 373-377 (2001)), thermal energydue to SPR absorption by the nanoparticles (Hirsch et al., PNAS, 100,13549-13554 (2003)), ultrasound (S. Coyle, et al., Phys. Rev. Let.87(17), 176801, (2001)) and other types of SPR generated energy. TheSPR-enhanced interactions between the nanoparticles and nearbysurrounding molecules can be million times or much higher than theseinteractions without SPR. Practically, without SPR, the only significantinteractions of nanoparticles with other substances occur when they arein direct contact, but the strength of these interactions is many ordersof magnitude weaker than in the presence of SPR. Therefore, prior artresearch findings indicate that for example antibacterial properties ofmaterials exist only when metal particles are in direct contact withbacteria (http://www.materials-edge.net/html/print.php?sid=95).

The enormous SPR-enhanced interactions of the nanoparticles with nearbyor in contact biological and chemical substances can be applied veryeffectively to environmental cleanup, corrosion protective technology,sanitization and other applications, which will have positive impact onhuman health and economics.

The SPR-enhanced interactions of the nanoparticles with surroundingmolecules are mainly catalytic interactions when nanoparticles areselected from the group of metals, metal oxides and semiconductors.Examples of catalytic reactions are shown on FIG. 1 and FIG. 2. When theenergy of light is sufficient to breakdown a metal complex (MX) (e.g.like it is in titanium dioxide, the UV light separates oxygen speciesfrom titanium), a metal (M) becomes the SPR source of electromagneticfields, ultrasound, heat and other forms of energy that induced newproperties of materials, and non-metal species (X) aggressively interactwith nearby biological and chemical substances. The SPR inducedelectromagnetic fields are very intense and electric field strength canbe as high as ˜10₇ V/m that can cause breakdown in condensed materialsincluding nearby biological and chemical substances (N. Bloembergen,“Laser-induced electric breakdown in solid”, IEEE. J. Quan. Electron.,10, pp.375-386 (1974); D. Stern, R. W. Schoenlein, C. A. Puliafito, E.T. Dobi R. Biringruber, J. G. Fujimoto, “Corneal ablation bynaonosecond, picosecond, and femtosecond lasers at 532 and 625 nm”,Arch. Ophthalrnol., 107,587-592 (1989)). The breakdown in condensedmaterials mainly is related to the separation of electric charges in thematerial area located nearby the SPR excited nanoparticle. Theseparation of electric charges induces new properties in the materiallike hydrophilicity/hydrophobicity (FIG. 3 and FIG. 4) and/oranti-adhering/adhering properties (FIG. 5). The SPR inducedhydrophilicity may remain for a long time (minutes, hours) in dielectricor semiconductor type materials. The SPR induced hydrophilicity in thematerial leads also to increasing hydrophobicity in the other areas ofthis material (FIG. 4.). Therefore, the proposed in the invention methodof the SPR induced hydrophilicity and hydrophobicity can be applied forvery efficient cleaning of dielectric and semiconducting materials likeglass, porcelain, silicon, silicon dioxide, plastic, textile natural andsynthetic fibers, but not limited only to them. The hydrophilicity andhydrophobicity properties of the material allows for easy cleaning ofinorganic and organic substances from the surface of this material. e.g.organic substances can be very easily cleaned by inorganic substancesand inorganic substances can be very easily cleaned by organicsubstances. The area of the SPR-enhanced hydrophilicity andhydrophobicity and the other SPR enhanced properties of material dependon the electric field strength of the SPR electromagnetic fields. As wasdemonstrated by Ditlbacher (Ditlbacher, H. et al., Appl. Phys. B 73,373-377 (2001)), SPR electromagnetic fields can exist at distance of 10microns from the SPR excited nanoparticles. Therefore, the area of SPRenhanced hydrophilicity and hydrophobicity and other SPR enhancedproperties of material can be as large as 100 square microns or more.The smallest area is limited by the nanoparticle size, and can be assmall as a few square nanometers.

Another embodiment of the present invention is a method of theSPR-enhanced anti-adhering and/or adhering properties of materials. TheSPR-enhanced anti-adhering properties of materials depend on separationof charges in the embedded nanoparticles under SPR absorption, strengthof SPR electromagnetic fields, amount of heat and other types of energyreleased by the nanoparticle after SPR absorption and also depend onelectronic structure and other properties of material. For example, themetal nanoparticle became very negatively charge after SPR absorptionand it will repel any nearby molecules with a negative charge (FIG. 5).Therefore, most biological negatively charged substances would havedifficulty to adhere to material surfaces with embedded metalnanoparticles. This SPR anti-adhering property of the materials isproposed in this invention to apply to contact lenses and surfaces ofmedical instruments (but not limited to them). The negatively chargedSPR excited metal nanoparticles have also adhering properties formolecules with positive charge. The SPR controlled adhesivity ofmaterials may have many applications and they are also a part of thepresent invention. One of many scenarios of the SPR controlledanti-adhering and adhering properties of the materials could be anapplication, in which UV light is used for the SPR-enhanced adheringproperties of the material, and red light is used for the SPR-enhancedanti-adhering properties of this material. For example, the UV lightinduced adhering properties of the material can be related to the SPRelectromagnetic fields-enhanced interaction with energy of theelectronic structures of the material molecules which leads tostiffening chemical bonds in the material and the red light inducedanti-adhering properties of this material can be related to generatedheat or other forms of energy by SPR absorbed nanoparticles.

The SPR enhanced anti-adhering contact lenses materials may also haveSPR-enhanced antibacterial properties. Both of these SPR-enhancedproperties of contact lenses described in the present invention maychange quality of life for many people wearing them. Additionally, acolor of the contact lenses can be selected by designing a size, shapeand coat of embedded nanoparticles.

Anyone of ordinary skill in the art will appreciate that the presentinvention considers nonlinear generation of SPR to enhanceantibacterial, anti-adhere/adhere, catalytic, hydrophilic/hydrophobic,spectral change, and biological and chemical decomposition properties ofmaterials. The nonlinear generation of SPR by one-photon excitation canbe expanded to nonlinear optical generation of SPR by two-photon,multi-photon, step-wise photons and up-conversion. It means that SPRgenerated in embedded nanoparticles by blue, visible and Near Infraredlight may enhance properties of materials in a similar way, as does UVlight. Therefore, our invention is not restricted to the specificwavelengths, and we propose to use light wavelengths for nonlinear SPRgeneration within the range of 0.001 nm to 20,000 nm. The opticalnonlinearity provides also the capability of three-dimensional localizedSPR-enhanced properties of the material with a spatial resolution atdiffraction limit. The method of the three-dimensionally SPR controlledproperties of materials may find many applications like controllingexternally chemical reactions in materials, using hydrophilicity versushydrophobicity to change material structure, providing adhering controlin materials, making a three-dimensional memory material, but the methodis not limited to these applications.

The SPR-enhanced antibacterial and anti-adhering properties of thematerials can be also applied to textile fabrics like personal clothing,filters, carpets, door mats, but not limited to them. The nanoparticlescan be embedded to natural or synthetic textile fabrics by wovenprocess, spraying colloidal nanoparticles on the fabrics, soakingfabrics in colloidal solution or by other methods. Some type ofnanoparticles embedded in personal clothing may stain the clothing, andtherefore these nanoparticles should be coated with a stain preventingmaterial. Usually, discolorations by nanoparticles are related tooxidation processes, and to inhibit these processes it is advisable tocover nanoparticles with a thin film of a protective material. Theprotective material may also help to optimize the best SPR-enhancedantimicrobial properties of materials.

Another embodiment in the present invention is a method of SPR-enhancedspectral changes in materials upon physical and biochemical changes ofthe environment surrounding these materials. In the method, spectralchanges of materials with embedded nanoparticles are induced andcontrolled by SPR and light. An example of the method applied tothermochromic properties of materials is described here in the twoscenarios. In scenario # 1, a material is embedded with a nanoparticlecomposite of a metal complex (MX) and another doped metal (N).Preferably the other metal (N) has an oxidation number higher than theoxidation number of a metal (M) in the metal complex (MX). Under SPRabsorption by the metal complexes (MX) and/or by the other metal (N),the metal complex (MX) remains as the complex as long as the temperatureof the nanoparticle is not high enough to break the complex. Above acertain temperature of the nanoparticle composite the complexdissociates, and a non-metal ligand in the complex (X) is attracted byanother metal (N) in the nanoparticle composite and forms a new complex(NX) with very different spectral properties (FIG. 6). In scenario # 2,the same nanoparticle composite as in the scenario # 1 generates heatupon SPR absorption that breaks the complex (MX) and the metal (M) andnon-metal ligand (M) have different spectral properties. In the scenario# 2, redissociation process occurs when the temperature of the materialnanoparticle decreases (FIG. 7). In scenarios # 1 and # 2, thecontribution of SPR electromagnetic fields and other forms of energygenerated by SPR are also considered a part of this invention.

Another embodiment in the present invention is a method of an additionalenhancement of SPR-enhanced properties of material by the presence of achemical substance, biological substance and/or drug. One of manyexamples of this embodiment can be the use of hydrogen peroxide on amaterial surface coated with metal nanoparticles (M) (FIG. 8). In thepresence of SPR and light the hydrogen peroxide molecules will decomposeto water molecules that under SPR will make complexes with the metalnanoparticles (M) creating hydrophilic properties of the material andthe released atomic oxygen molecules will very aggressively oxidizenearby molecules.

Anyone of ordinary skill in the art will appreciate that the presentinvention applies also to corrosion protective paints. The SPR-enhancedproperties of materials and/or the presence of chemical and/orbiological substances can be used to absorb and neutralize corrosioncausing substances. In this method, one of many scenarios is as follow.The nanoparticles embedded to a corrosion protective paint, underSPR-enhanced photocatalytic reactions with or without chemicaladditives, decompose corrosion causing substances. The photocatalyticreactions can be controlled by amount of nanoparticles and/or bychemical additives in the corrosion protective paint. In the paint,nanoparticles and chemical additives can also be covered byenvironmentally sensitive polymer that upon environmental conditionswill release a desired amount of the nanoparticles and chemicaladditives into the paints to decompose corrosion causing substances.This polymer may also release nanoparticles at a specific rate into thepaint in spite of environmental conditions. The paint may also provideindication about the progress of corrosion on material surfaces bydeveloping spectral signatures upon SPR-enhanced photocatalyticreactions of nanoparticles with the corrosion substances and/or withcorroded substances on material surfaces. The spectral signatures of thecorrosion progress can be measured visually or by instrument. Thepresented method can be applied to metal type surfaces and as well todielectric, semiconductor and other type surfaces.

Another embodiment of the present invention is a method of using surfaceplasmon resonance-enhanced properties of a material surface in a devicefor diagnostics purposes. The method also includes the enhancement offluorescence and Raman signal. Biological substances considered in thisinvention are selected from the group of a biomolecule, bacteria,protein, tissue, skin, cells, body fluid, bacteria, virus, pathogen,biochemical warfare agent (but not limited to them).

Chemical substances considered in this invention are selected from thegroup of an inorganic molecule, organic molecule, mixture of inorganicand organic molecules, drug, chemical warfare agent (but not limited tothem).

Medical devices considered in the invention are catheters, colonscopes,endoscopes, and any medical devices which are in contact with human oranimal body. Embedded nanoparticles considered in this invention are:metal, metallic composite, metal oxide, metallic salt, electricconductor, electric superconductor, electric semiconductor, dielectric,quantum dot, metal-dielectric composite, metal-semiconductor composite,metal-semiconductor-dielectric composite (but not limited to them). Theinvention considers the use for generation of SPR in the embeddednanoparticles electromagnetic radiation sources such as CW/pulsed andpolarized/non-polarized light sources like lamps, LEDs, single and/ormultiwavelength lasers for the SPR enhanced properties of the materials.However, SPR can also be generated by other techniques like sonic wavesor electrical technologies, electrostatic, ultrasound, magnetictechnologies. Therefore, these other techniques of generation SPR arealso considered as a part of the present invention, particularly ifthese techniques are combined with optical techniques.

1. A method of surface plasmon resonance-enhanced antimicrobial,anti-adhere, adhere, catalytic, hydrophilic, hydrophobic, spectralchange, biological and chemical decomposition properties of a materialcomprises of: a) a material; b) an embedded nanoparticle into saidmaterial; c) a biological substance or a chemical substance locatednearby said embedded nanoparticle; d) a surface plasmon resonance sourceexciting said embedded nanoparticle and irradiating said material,chemical substance and/or biological substance; e) a surface plasmonresonance excited embedded nanoparticle interacting with said material;f) a surface plasmon resonance excited embedded nanoparticle interactingwith nearby said biological substance and/or chemical substance.
 2. Themethod of claim 1, wherein said biological substance is selected fromthe group consisting of a biomolecule, amino acid, protein, tissue,non-tissue biological material, skin, cells, body fluid, bacteria,microbe, virus, pathogen, biochemical warfare agent, biological warfareagent.
 3. The method of claim 1, wherein said chemical substance is aninorganic molecule, organic molecule, mixture of inorganic and organicmolecules, drug, chemical warfare agent.
 4. The method of claim 1,wherein said embedded nanoparticle is a metal, metal oxide, metaldioxide, metallic salt, intermetallic alloy, transition metal, quantumdot, electric conductor, electric superconductor, electricsemiconductor, semiconductor doped with metal.
 5. The method of claim 4,wherein said embedded nanoparticle is selected from a group consistingof silver, silver oxide, silver ion, silver nitrate, ruthenium,platinum, palladium, cobalt, rhenium, rhodium, osmium, iridium, copper,aluminum, aluminum oxide, aluminum alloy, zinc, zinc oxide, nickel,chromium, magnesium, magnesium oxide, tungsten, iron, palladium, gold,titanium, titanium oxide, titanium dioxide, titania, alkaline earthmetal, selenium, cadmium, vanadium, vanadium oxide, molybdenum.
 6. Themethod of claim 4, wherein said nanoparticle is titanium dioxide.
 7. Themethod of claim 1, wherein said embedded nanoparticle has a size withina range of 0.1 nm to 200,000 nm in at least one of the dimensions. 8.The method of claim 7, wherein said nanoparticle is a thin film,colloid, fiber, metal island, nanowire, nanotube, empty shell, shellfilled with a conducting material, shell filled with a dielectricmaterial.
 9. The method of claim 1, wherein said embedded nanoparticleis a non-coated nanoparticle, coated nanoparticle.
 10. The method ofclaim 9, wherein said coated nanoparticle is coated by a semiconductor,conductor, biochemical substance, polymer, light sensitive polymer,disintegrating in time polymer, environmentally sensitive polymer. 11.The method of claim 10, wherein said coating material of said embeddednanoparticle has thickness within a range of 1 nm to 200,000 nm.
 12. Themethod of claim 1, wherein said material is a dielectric, conductor,semiconductor, silicon oxide, zeolite, mesoporous material, constructionmaterial, paint material, road pavement material, glass, ceramic,plastics, silicone, silica, adhesive material, corrosion protectivematerial, packaging material, contact lenses material, optical material,thermochromic material, quartz, polymer, polypropylene, aqueoussolution, organic solution, air, gas, textile fabric, cellulose basedmaterial, biological material.
 13. The method of claim 1, wherein saidembedded nanoparticle is located in said material from a surface of saidmaterial towards into said material within a distance of 0 nm to 200,000nm.
 14. The method of claim 1, wherein said biological substance or saidchemical substance are located nearby said embedded nanoparticle withina range of 0 nm to 200,000 nm.
 15. The method of claim 1, wherein saidsurface plasmon resonance source comprises a single or a multiple energysource of electromagnetic radiation, ultrasound, heat, electric,electrostatic, magnetic, radiation, mechanic.
 16. The method of claim15, wherein said surface plasmon resonance source is irradiating saidembedded nanoparticles and said material with intensity within the rangeof 0.00005 mW/cm² to 1000 TW/cm².
 17. The method of claim 15, whereinsaid electromagnetic radiation is selected from the group consisting ofa laser with single wavelength, laser with plurality wavelengths,semiconductor laser, pulsed laser, Q-switched laser, light emitteddiode, lamp, bioluminescence, sunlight, fluorescence, chemiluminescence,electroluminescence, luminescence, X-Rays.
 18. The method of claim 17,wherein said electromagnetic radiation source has a wavelength orwavelengths within a range of 0.001 nm to 20,000 nm,
 19. A method ofclaim 1, wherein said surface plasmon resonance source generates surfaceplasmon resonance in said embedded nanoparticles by said electromagneticradiation in a one-photon mode, two-photon mode, multi-photon mode,step-wise mode, up-conversion mode.
 20. A method of claim 1, whereinsaid surface plasmon resonance-enhanced antibacterial, anti-adhere,adhere, catalytic, hydrophilic, hydrophobic, spectral change, biologicaland chemical decomposition properties of said material are applied to aroad pavement, outdoor wall, internal wall, walkway, glass window,mirror, ceramic tile, sanitary unit, object for public use, carpet, rug,adhesive technology, paint, corrosion protective technology, medicaldevice, device, medical supply, contact lenses, glove, optical surface,glasses, goggle, medical implant, air filter, fluid filter, airfreshener, air humidifier, indoor air, air in commuting vehicle, airsystem in airplane, residential and commercial air conditioning andheating ventilation system, textile fabric, door mat, clothing, cleaningwater, surface cleaning technology, cleaning air, disinfectant product,antiseptic product, water supply line, water container, bathtub,whirlpool, Jacuzzi, swimming pool, dental waterline, food technology,food and beverage packaging technology animal food technology, householdcleaning product, kitchen product, product for pets, cosmetic product,hygiene product, medical bio-safety product, hair product, laundryproduct, pharmaceutical product for human, pharmaceutical product foranimal, surface preserving product, art preserving product, chemicalwarfare technology, biological warfare technology, memory technology,telecommunication technology.
 21. A method of claim 1 is applied tocontact lenses.
 22. A method of claim 1 is applied for chemical andbiological self-cleaning of said surface of said material.
 23. A methodof claim 1 is applied for an environmental cleanup, chemical warfareagent cleanup, biological warfare agent cleanup.
 24. A method of claim1, wherein an area of said surface plasmon resonance-enhanced propertiesof said material induced by said embedded nanoparticle is within a rangeof 10 nmsup2 to 10sup8 nmsup2.
 25. A method of claim 1, wherein saidsurface plasmon resonance-enhanced antibacterial, anti-adhere, adhere,catalytic, hydrophilic, hydrophobic, spectral change, biological andchemical decomposition properties of said material are controlled insaid material two-dimensionally or three-dimensionally.
 26. A method ofclaim 1, wherein said surface plasmon resonance-enhanced antibacterial,anti-adhere, adhere, catalytic, hydrophilic, hydrophobic, spectralchange, biological and chemical decomposition properties of saidmaterial are controlled by wavelengths of said electromagnetic radiationsource.
 27. A method of claim 1, wherein color of said material ismodified by a size and shape of said embedded nanoparticle.
 28. A methodof claim 1 and claim 20, wherein said surface plasmon resonance-enhancedantibacterial, anti-adhere, adhere, catalytic, hydrophilic, hydrophobic,spectral change, biological and chemical decomposition properties ofsaid material are applied in presence of said chemical substance,biological substance, drug.
 29. A method of claim 1 and claim 28 isapplied to a corrosion protective paint.
 30. A method of claim 29,wherein said corrosion protective paint changes its spectral propertiesupon a corrosion progress on said material surface.
 31. A method ofclaim 30, wherein spectral changes of said corrosion protective paintupon said corrosion progress on said material surface are measuredvisually or by a spectral instrument.
 32. A method of claim 29, whereinsaid corrosion protective paint releases an anti-corrosion activesubstance upon environmental conditions and/or time.
 33. A method ofclaim 1, wherein said surface plasmon resonance-enhanced properties ofmaterials including surface plasmon resonance-enhanced fluorescence andRaman are used in said device for diagnostics purposes.